Separation of mixtures of olefins and paraffins



April 20, 1943.

Filed Feb. 20, 1959 Fig. I.

. GulNoT 2,316,860

SEPARATION OF MIXTURES OF OLEFINS AND PARAFFINS 2 Sheets-Sheet l Attorney April 2o, 1943. H. M. GUINO'T 2,316,860

SEPARATION MIXTURES OF OLEFINS AND PARAFEINS Filed Feb. 2o, 1939 2 sheets-sheet 2 Fig. 2.

Conde/:sen

Patented Apr. 2o, 194:).

'SEPARATION OF RIIXTURES OF OLEFINS AND PARAFFIN S Henri Martin Guinot, Niort, Deux-Sevres, France; vested in the Alien Property Custodian Application February 20, 1939, Serial No. 257,539 In France March 25, 1938 1 claim. (ci. 2oz- 42) -44, and propene, the boiling point of which isv -47, cannot be separated by ordinary means.

Now it has been found that the separation of such olen-parain mixtures may be achieved by carrying out the distillation in the presence of sulphur dioxide, maintained in the liquid state by the establishment of a convenient temperature. For example, returning to the consideration of the particular substances mentioned above, it has been found that if a certain quantity of liquied sulphur dioxide is added to a mixture of propane and propene in liquid form, and the whole mixture is boiled, the vapours evolved are rich in sulphur dioxide and in propane but practically free from propene. If a careful distillation is carried o ut the removal of all of the propane contained in the initial mixture is achieved, the liquid residue being exclusively constituted by sulphur dioxide and pure propene.

A similar result would be obtained if the distillation were carried out under pressure, instead of treating the liquied gases under atmospheric pressure.

These observations are explained by the fact that the propane and the sulphur dioxide give, at allA pressures, an azeotropic mixture which, under the pressure of '7 kg. per cm.2 for example, contains about 22% of sulphur dioxide and which tends to behave as a head product. Propene on the contrary does not form an'azeotropic mixture with liquid sulphur dioxide, with which however, it is miscible in all proportions, even at a low temperature. Liquid sulphur dioxide retains propene strongly, whereas the mixtures of propane andsulphur dioxide separate into two layers.

The present invention therefore consists in a process for the separation of mixtures of olefins and paraflins in which the olen-parain mixture is distilled in the presence of liquid sulphur diis introduced, while slight heating is provided at the base of the column.

The olefin is absorbed by the sulphur dioxide whereas the paraflin escapes .at the upper part, mixedwith the sulphur dioxide in the form of an azeotropic mixture rich in hydrocarbon (approximately 78% under a pressure of 'l kgs. in the case of propene). After condensation this azeotropic mixture is sent to another column Working under pressure where it is treated with water, in the upper part thereof. By slightly heating the base of the column, the paraiiln, only slightly soluble in water, is removed by distillation, whereas the sulphur dioxide, miscible with the Water in all proportions and much less volatile than the hydrocarbon, is obtained at the base in the form of an aqueous solution; it is recovered by simple distillation from the aqueous solution and is returned to the circuit.

This treatment can be simplied by making the parain-SOz azeotropic mixture separate into two layers by decantation and by continuously returning the lower layer of sulphur dioxide to the principal column. As for the upper layer formed of parafiin containing a little SO2 in solution, it

vis freed from this latter by simple boiling, which leaves the pure paraffin as a residue.

Whatever the manner of treatment of the binary parain-SOz mixture may be, there is obtained at the base of the first column a liquid mixture of sulphur dioxide and oleiin which is separated into its constituents by simple rectification, the olen being obtained as the most volatile product.

'Ihe following examples, given in connection with 4the accompanying diagrammatic drawings, illustrate how the invention may be carried into practice.

`Example 1 A mixture of propane and propene, originating for example from the rectification of cracking gas, and contained in the tank I (Fig. 1) is sent, in the liquid state, by the pipe. 2, into the central portion of a distillation column 3 which is heated at the base and the plates of which are provided with liquid sulphur dioxide. The entire apparatus functions under a pressure of about 7 atm.

The vapours which rise in the column become progressively richer in propane. When they arrive at the top they possess the composition of the propane-SO2 azeotropic mixture having 78% of propane and including no more than traces of nronene.

On the contrary, the liquid which refluxes from plate to plate becomes progressively poorer in propane under the combined action of heat and the liquid sulphur dioxide in the lower half of the column, so that there flows away at the base of the column through the pipe 4, a liquid mixture of propene and sulphur dioxide.

The vapours obtained from the top of the column are condensed in 5. One part of the liquid thus formed is returned directly by the pipe 6 to the top of the column in order to insure the necessary reflux for the concentrating on the plates. The other part, corresponding to the quantity of propane to be withdrawn from the circuit, is cooled to about -8 in a brine condenser 'I and then sent to a separator 8 where the mixture separates in two layers, the lower layer, which is sulphur dioxide in an almost pure state is returned to the central portion of' the principal column by the pipe 9; the upper layer which is propane having a little sulphur dioxide in solution, is sent through the pipe I into the central portion of a column Il which is heated at the base and from the head of which is received the sulphurous acid in the form of a binary (i. e. azeotropic) mixture which is returned to the brine refrigerant 'l by the pipe l2,. i whereas pure propane flows from the base and their separation is easily effected in the order of their volatilities; propene is obtained at the head of column I4 and it is removed from the apparatus in the pure state by the pipe I5. At

the base of column I4 the sulphur dioxide is obtained, and it is returned to the manufacturing cycle by means of the pump I6 by the tube I1 and 9.

Example 2 The distillation of the mixture is carried out in the presence of SO2 as in Example 1 but instead of cooling the azeotropic mixture and allowing it to separate it is sent, directly it 'leaves the outlet of the condenser 5 (Fig. 2), to the central part of a small auxiliary column IB which receives at its head through the tube I9, a shower of pure water coming from the tank 20. The water descending from plate to plate dissolves the sulphur dioxide and entrains it rapidly towards the lower part of the column. The propane, however, which is insoluble in water and 'the boiling point of which is much lower than that of Water, is vaporised alone in the column. It arrives at the head of this latter in the pure state, from whence itis withdrawn through 2| after condensation in 22.

'I'he aqueous solution of sulphur dioxide which flows away from the base of the small column I8 through the pipe 23, is separated into its con-y stituents, by simple distillation in a second small column 24; the sulphur dioxide thus recovered being returned to theprincipal column by the pipes 25 and I'I.

The treatment of the mixture of sulphur dioxide and propene obtained at the base of the column 3 is eiiected as in Example l.

The process of the present invention is also particularly applicable to mixtures of ethane and ethene. Y l.

It is to be noted that the process andapparatus above described are operative inthe case of these olens which, at any given pressure..y

olefin will be obtained from the base of the column.

What I claim is:

A process for the separation of a mixture of olens and parains, which comprises introducing said mixture in liquid condition to near the central por-tion of a first distillationilolumn provided with plates, introducing sulphur dioxide into said column at a point slightly above the point of introduction of said mixture, applying heat to the base of said column, condensing the parailin-sulphur dioxide azeotropic mixture thus obtained, introducing said azeotropic mixture to near the central part of a rst auxiliary column, showering water through said rst auxiliary column,applying heat to base of said rst auxiliary column to obtain pure parailin as a head product and aqueous sulphur dioxide as a tail product, introducing said aqueous sulphur dioxide to near the central part of a second auxiliary column, distilling said aqueous sulphur dioxide within said second auxiliary column to obtain sulphur dioxide as a head product, returning said sulphur dioxide to said rst distillation column, removing said olefin as an oleiin-sulphur dioxide mixture from the foot of said rst distillation column, introducing said mixture to near the centre of a third auxiliary column, applying heat to the base of the said third auxiliary column, obtaining pure olen as a head product and obtaining sulphur dioxide as a. tail product and returning said sulphur dioxide to said irst distillation column.

HENRI MARTIN GUINOT. 

